U.S. patent number 10,233,200 [Application Number 15/681,750] was granted by the patent office on 2019-03-19 for organomodified monosilyl compound, its preparation and applications thereof.
This patent grant is currently assigned to Momentive Performance Matericals Inc.. The grantee listed for this patent is Momentive Performance Materials Inc.. Invention is credited to Narayan Mukherjee, George A Policello.
![](/patent/grant/10233200/US10233200-20190319-C00001.png)
![](/patent/grant/10233200/US10233200-20190319-C00002.png)
![](/patent/grant/10233200/US10233200-20190319-C00003.png)
![](/patent/grant/10233200/US10233200-20190319-C00004.png)
![](/patent/grant/10233200/US10233200-20190319-C00005.png)
![](/patent/grant/10233200/US10233200-20190319-C00006.png)
![](/patent/grant/10233200/US10233200-20190319-Parenopenst.png)
United States Patent |
10,233,200 |
Mukherjee , et al. |
March 19, 2019 |
Organomodified monosilyl compound, its preparation and applications
thereof
Abstract
Organomodified monosilyl compounds as defined herein exhibit
excellent resistance to hydrolysis over a wide range of pH and
excellent wetting properties. The organomodified monosilyl
compounds are advantageously employed as wetting agents in any of a
wide variety of products such as agrochemical compositions,
cosurfactants, coatings, personal care products and home care
products.
Inventors: |
Mukherjee; Narayan
(Croton-on-Hudson, NY), Policello; George A (Ossining,
NY) |
Applicant: |
Name |
City |
State |
Country |
Type |
Momentive Performance Materials Inc. |
Waterford |
NY |
US |
|
|
Assignee: |
Momentive Performance Matericals
Inc. (Waterford, NY)
|
Family
ID: |
63762942 |
Appl.
No.: |
15/681,750 |
Filed: |
August 21, 2017 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20190055271 A1 |
Feb 21, 2019 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01N
37/10 (20130101); A01N 25/30 (20130101); A01N
25/24 (20130101); C07F 7/081 (20130101); A01N
25/02 (20130101); A01N 25/30 (20130101); A01N
39/04 (20130101) |
Current International
Class: |
C07F
7/08 (20060101); A01N 25/24 (20060101); A01N
37/10 (20060101); A01N 25/02 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
0710500 |
|
Oct 1995 |
|
EP |
|
2014186658 |
|
Nov 2014 |
|
WO |
|
Other References
International Search Report and Written Opinion dated Dec. 20,
2018. cited by applicant.
|
Primary Examiner: Brooks; Clinton A
Assistant Examiner: Adzamli; Kofi
Attorney, Agent or Firm: Ostroff; Joseph S.
Claims
The invention claimed is:
1. An organomodified monosilyl compound of the general formula:
R.sup.1--Si(CH.sub.3).sub.2--Z wherein: R.sup.1 is a branched
monovalent hydrocarbon group of from 5 to 8 carbon atoms containing
at least two methyl groups; Z is R.sup.2 or R.sup.3; --R.sup.2 is
CH.sub.2CH.sub.2CH.sub.2--OC.sub.2H.sub.4--O).sub.a(C.sub.3H.sub.6O).sub.-
b(C.sub.4H.sub.8O).sub.c--R.sup.4 in which R.sup.4 is hydrogen, a
linear or branched monovalent hydrocarbon group of from 1 to about
4 carbon atoms or an acyl group, subscript a is from 1 to about 20,
subscript b is from 0 to about 19, subscript c is from 0 to about
19 and the sum of subscripts a, b and c is from 1 to about 20; and,
R.sup.3 is
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2--N.sup.+(CH.sub.3).sub.2--R-
.sup.5 [X.sup.-] in which R.sup.5 is a linear or branched
hydrocarbon group of from 1 to about 4 carbon atoms or an acetyl
group and X.sup.- is a saturated or unsaturated carboxylate anion
of from 2 to about 22 carbon atoms containing 0 to 2 hydroxyl
groups.
2. The organomodifed monosilyl compound of claim 1, wherein R.sup.1
is a branched alkyl group
CR.sup.6R.sup.7R.sup.8(CR.sup.9R.sup.10).sub.m(CR.sup.11R.sup.12).sub.nCH-
R.sup.13CH.sub.2-- in which R.sup.6, R.sup.7, R.sup.8, R.sup.9,
R.sup.10, R.sup.11, R.sup.12 and R.sup.13 each independently is
hydrogen or methyl, from 2 to 4 of R.sup.6, R.sup.7, R.sup.8,
R.sup.9, R.sup.10, R.sup.11, R.sup.12 and R.sup.13 are methyl and
subscripts m and n each independently is 0 or 1.
3. The organomodified monosilyl compound of claim 2, wherein
R.sup.1 contains from 2 to 4 methyl groups, CR.sup.6R.sup.7R.sup.8
is H.sub.3C--, (H.sub.3C).sub.2CH-- or (H.sub.3C).sub.3C--,
subscripts m and/or n are 0, Z is R.sup.2 and R.sup.2 is
--CH.sub.2CH.sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.a(C.sub.3H.sub.6O).s-
ub.b--R.sup.4 in which R.sup.4 is hydrogen, linear or branched
alkyl of from 1 to 4 carbon atoms or an acyl group, subscript a is
from 1 to about 20, subscript b is from 0 to about 10 and the sum
of subscripts a and b is from 1 to about 20.
4. The organomodified monosilyl compound of claim 3, wherein
subscript a is from 2 to about 15.
5. The organomodified monosilyl compound of claim 4, wherein
subscript b is from 0 to about 6 and the sum of subscripts a and b
is from 2 to about 15.
6. The organomodified monosilyl compound of claim 3, wherein
subscript a is from 4 to about 10.
7. The organomodified monosilyl compound of claim 6, wherein
subscript b is from 0 to about 4 and the sum of subscripts a and b
is from about 4 to about 10.
8. The organomodified monosilyl compound of claim 3, wherein
subscript b is from 0 to about 6.
9. An agrochemical composition comprising a wetting agent-effective
amount of at least one organomodified monosilyl compound of claim
8.
10. An agrochemical composition comprising a wetting
agent-effective amount of at least one organomodified monosilyl
compound of claim 3.
11. The organomodified monosilyl compound of claim 2, wherein
R.sup.1 contains from 2 to 4 methyl groups, CR.sup.6R.sup.7R.sup.8
is H.sub.3C--, (H.sub.3C).sub.2CH-- or (H.sub.3C).sub.3C--, m
and/or n are 0 or 1, Z is R.sup.3 and R.sup.3 is
--CH.sub.2CH.sub.2CH.sub.2--O--CH.sub.2(OH)--CH.sub.2--N.sup.+(CH.sub.3).-
sub.2--R.sup.5 [X.sup.-] in which R.sup.5 is a linear or branched
alkyl of from 1 to about 4 carbon atoms.
12. An agrochemical composition comprising a wetting
agent-effective amount of at least one organomodified monosilyl
compound of claim 11.
13. The organomodified monosilyl compound of claim 2, wherein
R.sup.1 contains from 2 to 4 methyl groups, CR.sup.1R.sup.2R.sup.3
is (H.sub.3C).sub.2CH-- or (H.sub.3C).sub.3C--, m is 0 or 1, n is
0, Z is R.sup.3 and R.sup.3 is
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)--CH.sub.2--N.sup.+(CH.sub.3).sub.2--
-R.sup.5 [X.sup.-] in which R.sup.5 is a linear or branched alkyl
group of from 1 to about 4 carbon atoms and X.sup.- is a
carboxylate anion of from 2 to about 10 carbon atoms and from 0 to
2 hydroxyl groups.
14. The organomodified compound of claim 13, wherein X.sup.- is a
carboxylate anion of from 2 to about 6 carbon atoms and from 0 to 2
hydroxyl groups.
15. An agrochemical composition comprising a wetting
agent-effective amount of at least one organomodified monosilyl
compound of claim 13.
16. The organomodified monosilyl compound of claim 2 which is at
least one ether- or polyether-modified monosilyl compound selected
from the group consisting of: TABLE-US-00011
CR.sup.6R.sup.7R.sup.8(CR.sup.9R.sup.10).sub.m(CR.sup.11R.sup.12).sub.n--C-
HR.sup.13--CH.sub.2--Si(CH.sub.3).sub.2-- --Z
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.- 2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2- CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5CH.sub.3
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.-
2CH.sub.2--O(CH.sub.2H.sub.4O).sub.5(C.sub.3H.sub.6O).sub.2.5H
(CH.sub.3).sub.2CHCH(CH.sub.3)CH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
-- -CH.sub.2CH.sub.2CH.sub.2--O--(CH.sub.2CH.sub.2O).sub.4H
H.sub.3CCH.sub.2CH(CH.sub.3)CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.su- b.2CH.sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
H.sub.3CCH.sub.2C(CH.sub.3).sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--- CH.sub.2CH.sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
(H.sub.3C).sub.2CHCH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.- sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5CH.sub.3
H.sub.3CCH.sub.2C(CH.sub.3).sub.2C(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2---
--CH.sub.2CH.sub.2CH.sub.2--O(CH.sub.2H.sub.4O).sub.5(C.sub.3H.sub.6O).su-
b.2.5H
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.- 2CH.sub.2CH.sub.2--O--(CH.sub.2CH.sub.2O).sub.5H
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2- CH.sub.2--O--CH.sub.2CH.sub.2OH
(H.sub.3C).sub.2CHCH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.- sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2-
CH.sub.2--O(CH.sub.2H.sub.4O).sub.5(C.sub.3H.sub.6O).sub.2.5H.
17. An agrochemical composition comprising a wetting
agent-effective amount of at least one organomodified monosilyl
compound of claim 16.
18. The organomodified monosilyl compound of claim 2 which is at
least one quaternary ammonium-modified monosilyl compound selected
from the group consisting of: TABLE-US-00012
CR.sup.6R.sup.7R.sup.8(CR.sup.9R.sup.10).sub.m(CR.sup.11R.sup.12).sub.n--C-
HR.sup.13--CH.sub.2--Si(CH.sub.3).sub.2-- --Z
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.-
2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3[CH.sub.3CH.sub.2COO.sup.-]
(H.sub.3C).sub.2CHCH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.-
sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3[CH.sub.3CH.sub.2COO.sup.-]
H.sub.3CCH.sub.2C(CH.sub.3).sub.2C(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2---
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3[(CH.sub.2OH).sub.2(CH.sub.3)C--COO.sup.-]
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2-
CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3[CH.sub.2(OH).sub.2(CH.sub.3)C--COO.sup.-]
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2-
CH.sub.2--O--CH.sub.2CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.2CH.sub.2OH[(CH.sub.2OH).sub.2(CH.sub.3)C--COO.sup.-]
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.-
2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.3CH.sub.2COO.sup.-]
(H.sub.3C).sub.2CHCH(CH.sub.3)CH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--
-CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-]
H.sub.3CCH.sub.2CH(CH.sub.3)CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.su-
b.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-]
H.sub.3CCH.sub.2C(CH.sub.3).sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
---
CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-]
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.-
2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2CH.sub.2COO.sup.-]
H.sub.3CC(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2--CH.sub.2--Si(CH.sub.3).-
sub.2--
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub-
.2-- CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-].
19. An agrochemical composition comprising a wetting
agent-effective amount of at least one organomodified monosilyl
compound of claim 2.
20. An agrochemical composition, cosurfactant, coating, personal
care product or home care product comprising a wetting
agent-effective amount of at least one organomodified monosilyl
compound of claim 1.
21. An agrochemical composition comprising a wetting
agent-effective amount of at least one organomodified monosilyl
compound of claim 18.
Description
FIELD OF THE INVENTION
The present invention relates to organomodified monosilyl compounds
exhibiting resistance to hydrolysis over a wide pH range. More
particularly, the present invention relates to hydrolysis-resistant
organomodified monosilyl compounds having resistance to hydrolysis
over a pH ranging from about 2 to about 12. The present invention
also relates to such hydrolysis-resistant organomodified monosilyl
compounds as components of agricultural, cosmetic, home care and
coating compositions.
BACKGROUND OF THE INVENTION
The topical application of liquid compositions to the surfaces of
both animate and inanimate objects to effect a desired change
involve processes of controlling wetting, spreading, foaming,
detergency, and the like. When used in aqueous solutions to improve
the delivery of active ingredients to the surface being treated,
trisiloxane-type compounds have been found to be useful in enabling
the control of these processes to achieve the desired effect.
However, trisiloxane compounds can only be used within a narrow pH
range, one ranging from a slightly acidic pH of 6 to a very mildly
basic pH of 7.5. Outside this narrow pH range, trisiloxanes are not
stable to hydrolysis, undergoing rapid decomposition.
Silicon based surfactants that are stable to hydrolysis over a wide
pH range are very desirable as such compounds would allow for
compositions providing more effective topical application to the
surfaces of both animate and inanimate objects, the use of smaller
quantities of water and/or an increase in the effectiveness of
agricultural sprays.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided an
organomodified monosilyl compound of the general formula:
R.sup.1--Si(CH.sub.3).sub.2--Z wherein:
R.sup.1 is branched monovalent hydrocarbon group of from 5 to 8
carbon atoms containing at least two methyl groups;
Z is R.sup.2 or R.sup.3;
R.sup.2 is
CH.sub.2CH.sub.2CH.sub.2--OC.sub.2H.sub.4--O).sub.a(C.sub.3H.sub.6O).sub.-
b(C.sub.4H.sub.8O).sub.c--R.sup.4 in which R.sup.4 is hydrogen, a
linear or branched monovalent hydrocarbon group of from 1 to about
4 carbon atoms or an acyl group, subscript a is from 1 to about 20,
subscript b is from 0 to about 19, subscript c is from 0 to about
19 and the sum of subscripts a, b and c is from 1 to about 20;
and,
R.sup.3 is
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2--N.sup.+(CH.sub.3).sub.2--R-
.sup.5 [X.sup.-] in which R.sup.5 is a linear or branched
hydrocarbon group of from 1 to about 4 carbon atoms or an acetyl
group and X.sup.- is a saturated or unsaturated carboxylate anion
of from 2 to about 22 carbon atoms optionally containing 1 or 2
hydroxyl groups.
The organomodified monosilyl compound of the invention may be
incorporated in numerous types of compositions, e.g., agricultural
compositions, cosmetic compositions, home care compositions and
coating compositions, to which its excellent stability over a wide
range of pH and outstanding wetting properties impart considerable
functional advantages.
DETAILED DESCRIPTION OF THE INVENTION
In the specification and claims herein, the following terms and
expressions are to be understood as indicated.
The singular forms "a," "an," and "the" include the plural, and
reference to a particular numerical value includes at least that
particular value, unless the context clearly dictates
otherwise.
Other than in the working examples or where otherwise indicated,
all numbers expressing amounts of materials, reaction conditions,
time durations, quantified properties of materials, and so forth,
stated in the specification and claims are to be understood as
being modified in all instances by the term "about".
All methods described herein may be performed in any suitable order
unless otherwise indicated herein or otherwise clearly contradicted
by context. The use of any and all examples, or exemplary language
(e.g., "such as") provided herein, is intended merely to better
illuminate the invention and does not pose a limitation on the
scope of the invention unless otherwise claimed.
No language in the specification should be construed as indicating
any non-claimed element as essential to the practice of the
invention.
The terms, "comprising," "including," "containing," "characterized
by," and grammatical equivalents thereof are inclusive or
open-ended terms that do not exclude additional, unrecited elements
or method steps, but will also be understood to include the more
restrictive terms "consisting of" and "consisting essentially
of."
It will be understood that any numerical range recited herein
includes all sub-ranges within that range and any combination of
the various endpoints of such ranges or sub-ranges.
As used herein, integer values of stoichiometric subscripts refer
to molecular species and non-integer values of stoichiometric
subscripts refer to a mixture of molecular species on a molecular
weight average basis, a number average basis or a mole fraction
basis.
It will be further understood that any compound, material or
substance which is expressly or implicitly disclosed in the
specification and/or recited in a claim as belonging to a group of
structurally, compositionally and/or functionally related
compounds, materials or substances includes individual
representatives of the group and all combinations thereof.
The term "adjuvant" means any composition, material or substance
which increases the efficacy of a bioactive material.
The term "bioactive" refers to an agricultural chemical or
material, including but not limited to pesticides, e.g.,
herbicides, fungicides, insecticides, acaricides and molluscides;
plant nutrients; defoliants; and, plant growth regulators.
The expression "hydrocarbon group" means any hydrocarbon from which
one or more hydrogen atoms has been removed and is inclusive of
alkyl, alkenyl, alkynyl, cyclic alkyl, cyclic alkenyl, cyclic
alkynyl, aryl, aralkyl and arenyl groups and is inclusive of
hydrocarbon groups containing at least one heteroatom.
The term "alkyl" means any monovalent, saturated straight, branched
or cyclic hydrocarbon group; the term "alkenyl" means any
monovalent straight, branched, or cyclic hydrocarbon group
containing one or more carbon-carbon double bonds where the site of
attachment of the group can be either at a carbon-carbon double
bond or elsewhere therein; and, the term "alkynyl" means any
monovalent straight, branched, or cyclic hydrocarbon group
containing one or more carbon-carbon triple bonds and, optionally,
one or more carbon-carbon double bonds, where the site of
attachment of the group can be either at a carbon-carbon triple
bond, a carbon-carbon double bond or elsewhere therein. Examples of
alkyls include methyl, ethyl, propyl and isobutyl. Examples of
alkenyls include vinyl, propenyl, allyl, methallyl, ethylidenyl
norbornane, ethylidene norbomyl, ethylidenyl norbornene and
ethylidene norbornenyl. Examples of alkynyls include acetylenyl,
propargyl and methylacetylenyl.
In some embodiments of organomodified monosilyl compound
R.sup.1--Si(CH.sub.3).sub.2--Z, R.sup.1 is a branched alkyl group
CR.sup.6R.sup.7R.sup.8(CR.sup.9R.sup.10).sub.m(CR.sup.11R.sup.12).sub.nCH-
R.sup.13CH.sub.2-- in which R.sup.6, R.sup.7, R.sup.8, R.sup.9,
R.sup.10, R.sup.11, R.sup.12 and R.sup.13 each independently is
hydrogen or methyl, from 2 to 4 of R.sup.6, R.sup.7, R.sup.8,
R.sup.9, R.sup.10, R.sup.11, R.sup.12 and R.sup.13 are methyl and
subscripts m and n each independently is 0 or 1.
In other embodiments of organomodified monosilyl compound
R.sup.1--Si(CH.sub.3).sub.2--Z, R.sup.1 contains from 2 to 4 methyl
groups, CR.sup.6R.sup.7R.sup.8 is H.sub.3C--, (H.sub.3C).sub.2CH--
or (H.sub.3C).sub.3C--, subscripts m and/or n are 0, Z is R.sup.2
and R.sup.2 is
--CH.sub.2CH.sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.a(C.sub.3HO).sub.b---
R.sup.4 in which R.sup.4 is hydrogen, linear or branched alkyl of
from 1 to 4 carbon atoms or an acyl group, subscript a is from 1 to
about 20, preferably from 2 to about 15 and more preferably from 4
to about 10, subscript b is 0 or from 1 to about 10, preferably 0
or from 1 to about 6 and more preferably 0 or from 1 to about 4,
and the sum of subscripts a and b is from 1 to about 20, preferably
from 2 to about 15 and more preferably from 4 to about 10.
In still other embodiments of organomodified monosilyl compound
R.sup.1--Si(CH.sub.3).sub.2--Z, R.sup.1 contains from 2 to 4 methyl
groups, CR.sup.6R.sup.7R.sup.8 is H.sub.3C--, (H.sub.3C).sub.2CH--
or (CH.sub.3).sub.3C--, m is 0 or 1, n is 0, Z is R.sup.2 and
R.sup.2 is
--CH.sub.2CH.sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.a--R.sup.4 in
which R.sup.4 is hydrogen, linear or branched alkyl of from 1 to 4
carbon atoms or an acyl group, and subscript a is from 1 to about
20, preferably from 2 to about 15 and more preferably from 4 to
about 10.
In further embodiments of organomodified monosilyl compound
R.sup.1--Si(CH.sub.3).sub.2--Z, CR.sup.6R.sup.7R.sup.8 is
H.sub.3C--, (H.sub.3C).sub.2CH-- or (H.sub.3C).sub.3C--, m and/or n
are 0 or 1, Z is R.sup.3 and R.sup.3 is
--CH.sub.2CH.sub.2CH.sub.2--O--CH.sub.2(OH)--CH.sub.2--N.sup.+(CH.sub.3).-
sub.2--R.sup.5 [X.sup.-] in which R.sup.5 is a linear or branched
alkyl of from 1 to about 4 carbon atoms and X.sup.- is as
previously defined.
In still further embodiments of organomodified monosilyl compound
R.sup.1--Si(CH.sub.3).sub.2--Z, R.sup.1 contains from 2 to 4 methyl
groups, CR.sup.1R.sup.2R.sup.3 is (H.sub.3C).sub.2CH-- or
(H.sub.3C).sub.3C--, m is 0 or 1, n is 0, Z is R.sup.3 and R.sup.3
is
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)--CH.sub.2--N.sup.+(CH.sub.3).sub.2--
-R.sup.5 [X.sup.-] in which R.sup.5 is a linear or branched alkyl
group of from 1 to about 4 carbon atoms and X.sup.- is a
carboxylate anion of from 2 to about 22 carbon atoms, preferably
from 2 to about 10 carbon atoms and more preferably from 2 to 6
carbon atoms, optionally containing 1 or 2 hydroxyl groups.
In particular embodiments of the organomodified monosilyl compound
herein, X.sup.- is the anion of: a monocarboxylic acid such as
acetic acid, propionic acid or butyric acid; a dicarboxylic acid
such as succinic acid, maleic acid or oxalic acid; a tricarboxylic
acid; an alpha-hydroxy acid such as glycolic acid, lactic acid,
citric acid or mandelic acid; a beta-hydroxy acid such as a
hydroxypropionic acid, salicylic acid, carnitine, .beta.-Hydroxy
.beta.-methylbutyric acid or 3-hydroxybutyric acid; a dihydroxy
acid such as dimethylol propionic acid; or, a saturated or
unsaturated fatty acid such as caprylic acid, capric acid, caproic
acid, oleic acid, myristoleic acid, stearic acid, linoleic acid or
erucic acid.
A. Method for Preparing the Organomodified Monosilyl Compound
Organomodified monosilyl compounds of the invention can be prepared
by any of several synthesis processes the requirements of which are
well known in the art.
According to one method of preparation of organomodified monosilyl
compounds R.sup.1--Si(CH.sub.3).sub.2--Z of the invention, at least
one branched alkene is reacted under catalytic hydrosilylation
reaction conditions with dimethylsilylchloride to provide a
chlorosilane adduct which is then made to undergo reduction to
provide the corresponding silylhydride intermediate. Branched
alkenes that are useful in preparing the foregoing chlorosilane
adduct and silylhydride intermediate used in the preparation of
organomodified monosilyl compounds R.sup.1--Si(CH.sub.3).sub.2--Z
herein include, e.g., the following and mixtures thereof:
TABLE-US-00001 (H.sub.3C).sub.2CHCH.sub.2CH.dbd.CH.sub.2
H.sub.3CCH.sub.2C(CH.sub.3)CH.db- d.CH.sub.2 4-methyl-1-pentene
3-methyl-1-pentene (H.sub.3C).sub.3CCH.dbd.CH.sub.2
H.sub.3CCH.sub.2C(CH.sub.3).sub.2CH.dbd.C- H.sub.2
3,3-dimethyl-1-butene 3,3-dimethy1-1-pentene
(H.sub.3C).sub.2CHCH.dbd.CH.sub.2
(H.sub.3C).sub.2CHCH(CH.sub.3).dbd.CH.su- b.2 3-methyl-1-butene
2,3-dimethyl-1-butene
(H.sub.3C).sub.2CHC(CH.sub.3)C(CH.sub.3).dbd.CH.sub.2
H.sub.3CCH.sub.2C(CH- .sub.3).sub.2C(CH.sub.2)
2,3,4-trimethyl-1-pentene 2,3,3-trimethyl-1-pentene
H.sub.3CCH.sub.2C(CH.sub.3).dbd.CH.sub.2
(HC.sub.3).sub.3CCH(CH.sub.3)CH-C- H.sub.2 2-methyl-1-butene
3,4,4-trimethyl-1-pentene (H.sub.3C).sub.3CC(CH.sub.3).dbd.CH.sub.2
H.sub.3CCH.sub.2CH.sub.2CH(CH.su- b.3).dbd.CH.sub.2
2,3,3-trimethyl-1-butene 2,4,4-trimethy1-1-butene
(H.sub.3C).sub.3CCH.sub.2CH.dbd.CH.sub.2
H.sub.3CCH(CH.sub.3)CH.sub.2CH.su- b.2CH.dbd.CH.sub.2
4,4-dimethyl-1-pentene 5-methyl-1-hexene
(H.sub.3C).sub.3CC(CH.sub.3).dbd.CH.sub.2
H.sub.3CC(CH.sub.3).sub.2CH.sub.- 2CH.sub.2CH.dbd.CH.sub.2
2,3,3-trimethyl-1-butene 5,5-dimethyl-1-hexene
Reduction of the chlorosilane adduct, including mixtures thereof,
to provide the silylhydride intermediate(s) can be conveniently
carried out employing any of various metal complexes as is well
known in the art, e.g., complexes of such metals as aluminum,
lithium, nickel, palladium or platinum. Many types of aluminum
catalysts for halosilane reduction are known and such complexes may
be used to generate the hydride intermediate herein. In one
embodiment, the metal complex is the organoaluminium compound
sodium bis(2-methoxyethyl) aluminum hydride, commercially available
as Vitride (Vertellus) or Red-Al (Sigma-Aldrich).
Reaction of the hydride intermediate(s) with one or more allyl- or
methallyl-ethers or polyethers, e.g., of the general formula
H.sub.2C.dbd.CR.sup.13CH.sub.2--O--(C.sub.2H.sub.4O).sub.a(C.sub.3H.sub.6-
O).sub.b(C.sub.4H.sub.8O).sub.c--R.sup.4, in which R.sup.4 is
hydrogen or methyl and R.sup.13 and subscripts a, b and c are as
previously defined, is carried out under catalytic hydrosilylation
reaction conditions to provide ether/polyether-modified monosilyl
compounds of the invention.
Suitable olefinically modified ethers/polyethers, including
mixtures thereof, that may be reacted with the silyl hydride
intermediate to provide ether/polyether-modified monosilyl
compounds of the invention include allyl propyl ether, methallyl
propyl ether, polyethyleneglycol allylether, polyethyleneglycol
polypropyleneglycol allylether, polypropyleneglycol allyl ether,
methoxy polyethyleneglycol allylether, methoxy polyethyleneglycol
polypropyleneglycol allylether, butoxy polyethyleneglycol
polyproplylene glycol allylether, methoxy polypropyleneglycol
allylether, butoxy polypropyleneglycol allylether,
polyethleneglycol polybutyleneglycol allylether, polyethyleneglycol
polypropyleneglycol polybutyleneglycol allylether, and their
mixtures. The allyl- and methallyl-terminated polyethers include
those of the random and block types.
Hydrosilylation catalysts and their use are well known in the art
and include complexes of such metals as rhodium, ruthenium,
palladium, osmium, iridium and platinum. Many types of
platinum-containing hydrosilylation catalyst can be used herein,
e.g., those having the formula PtCl.sub.2olefin and
HPtCl.sub.3olefin as described in U.S. Pat. No. 3,159,601, hereby
incorporated by reference. Other platinum-containing
hydrosilylation catalyst include complexes of chloroplatinic acid
with up to 2 moles per gram of platinum and an alcohol, ether,
aldehyde and mixtures thereof as described in U.S. Pat. No.
3,220,972, hereby incorporated by reference. Additional
platinum-containing hydrosilylation catalysts useful in preparing
the organomodified silylated compounds of the present invention are
described in U.S. Pat. Nos. 3,715,334, 3,775,452 and 3,814,730
(Karstedt's catalyst), hereby incorporated by reference. Further
background concerning hydrosilylation may be found in J. L. Spier,
"Homogeneous Catalysis of Hydrosilylation by "Transition Metals",
in Advances in Organometallic Chemistry, volume 17, pages 407
through 447, F. G. A. Stone and R. West editors, published by
Academic Press (New York, 1979), hereby incorporated by reference.
Those skilled in the art can readily determine the effective amount
of catalyst for a given hydrosilylation reaction. Generally, an
amount of hydrosilylation catalyst ranging from about 0.1 to 50
parts per million by weight of the desired hydrosilylation will be
satisfactory.
Illustrated for 3,3-dimethyl-but-1-ene, one process for preparing
ether/polyether-modified monosilyl compounds of the invention can
be considered to proceed as follows:
##STR00001##
The following ether/polyether-modified monosilyl compounds of the
invention may be prepared in accordance with the synthesis
described above:
TABLE-US-00002
CR.sup.6R.sup.7R.sup.8(CR.sup.9R.sup.10).sub.m(CR.sup.11R.sup.12).sub.n--C-
HR.sup.13--CH.sub.2--Si(CH.sub.3).sub.2-- --Z
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.- 2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2- CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5CH.sub.3
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.-
2CH.sub.2--O(CH.sub.2H.sub.4O).sub.5(C.sub.3H.sub.6O).sub.2.5H
(CH.sub.3).sub.2CHCH(CH.sub.3)CH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
-- -CH.sub.2CH.sub.2CH.sub.2--O--(CH.sub.2CH.sub.2O).sub.4H
H.sub.3CCH.sub.2CH(CH.sub.3)CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.su- b.2CH.sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
H.sub.3CCH.sub.2C(CH.sub.3).sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--- CH.sub.2CH.sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
(H.sub.3C).sub.2CHCH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.- sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5CH.sub.3
H.sub.3CCH.sub.2C(CH.sub.3).sub.2C(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2---
--CH.sub.2CH.sub.2CH.sub.2--O(CH.sub.2H.sub.4O).sub.5(C.sub.3H.sub.6O).su-
b.2.5H
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.- 2CH.sub.2CH.sub.2--O--(CH.sub.2CH.sub.2O).sub.5H
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2- CH.sub.2--O--CH.sub.2CH.sub.2OH
(H.sub.3C).sub.2CHCH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.- sub.2CH.sub.2--O--(C.sub.2H.sub.4O).sub.7.5H
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2-
CH.sub.2--O(CH.sub.2H.sub.4O).sub.5(C.sub.3H.sub.6O).sub.2.5H
According to another process for preparing organomodified monosilyl
compounds R.sup.1--Si(CH.sub.3).sub.2--Z, specifically, one which
provides quaternary-modified monosilyl compounds of the invention,
the silyl hydride intermediate obtained as shown above is reacted
with glycidyl ether and/or methallyl glycidyl ether followed by
ring-opening reaction with a quaternary alkyldimethyl ammonium salt
or quat-forming mixture of the desired acid X and tertiary
alkyldimethylamine as illustrated by the reaction scheme:
##STR00002##
The following quaternary ammonium-modified monosilyl compounds
R.sup.1--Si(CH.sub.3).sub.2--Z of the invention may be prepared in
accordance with the synthesis described above:
TABLE-US-00003
CR.sup.6R.sup.7R.sup.8(CR.sup.9R.sup.10).sub.m(CR.sup.11R.sup.12).sub.n--C-
HR.sup.13--CH.sub.2--Si(CH.sub.3).sub.2-- --Z
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.-
2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3[CH.sub.3CH.sub.2COO.sup.-]
(H.sub.3C).sub.2CHCH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.-
sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3[CH.sub.3CH.sub.2COO.sup.-]
H.sub.3CCH.sub.2C(CH.sub.3).sub.2C(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2---
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3R[(CH.sub.2OH).sub.2(CH.sub.3)C--COO.sup.-]
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2-
CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3[(CH.sub.2OH).sub.2(CH.sub.3)C--COO.sup.-]
TABLE-US-00004
CR.sup.6R.sup.7R.sup.8(CR.sup.9R.sup.10).sub.m(CR.sup.11R.sup.12).sub.n--C-
HR.sup.13--CH.sub.2--Si(CH.sub.3).sub.2-- --Z
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.2-
CH.sub.2--O--CH.sub.2CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.2CH.sub.2OH[(CH.sub.2OH).sub.2(CH.sub.3)C--COO.sup.-]
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.-
2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.3CH.sub.2COO.sup.-]
(H.sub.3C).sub.2CHCH(CH.sub.3)CH(CH.sub.3)CH.sub.2--Si(CH.sub.3).sub.2--
--
-CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-]
H.sub.3CCH.sub.2CH(CH.sub.3)CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.su-
b.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-]
H.sub.3CCH.sub.2C(CH.sub.3).sub.2CH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
---
CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-]
(H.sub.3C).sub.2CHCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--
--CH.sub.2CH.sub.-
2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--
CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2CH.sub.2COO.sup.-]
H.sub.3CC(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2--CH.sub.2--Si(CH.sub.3).-
sub.2--
--CH.sub.2CH.sub.2CH.sub.2--O--CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub-
.2-- CH.sub.2CH.sub.3 [CH.sub.2(OH)CH.sub.2COO.sup.-]
B. Compositions Containing Organomodified Monosilyl Compound
R.sup.1--Si(CH.sub.3).sub.2--Z
The organomodified monosilyl compound of the present invention may
be utilized in a variety of forms: as liquid solutions, dispersions
of solids in liquids, dispersions of liquids in liquids, solid
mixtures or solid solutions, etc., either separately or in
combinations thereof. Compositions will generally contain a wetting
agent-effective amount of one or more organomodified silyl
compounds R.sup.1--Si(CH.sub.3).sub.2--Z of the invention, e.g.,
depending on the particular purpose or use of a given composition,
from about 0.01 to about 99, and advantageously from about 0.1 to
about 50 weight percent of the organomodified silyl compound(s)
based on the weight of the composition.
1. Agrochemical Compositions
Many pesticide applications require the addition of an adjuvant to
the spray mixture to provide wetting and spreading on foliar
surfaces. Often that adjuvant is a surfactant, which can perform a
variety of functions, such as increasing spray droplet retention on
difficult to wet leaf surfaces, enhance spreading to improve spray
coverage, or to provide penetration of the herbicide into the plant
cuticle. These adjuvants are provided either as a tank-side
additive or used as a component in pesticide formulations.
Typical uses for pesticides include agricultural, horticultural,
turf, ornamental, home and garden, veterinary and forestry
applications. The pesticidal compositions of the present invention
also include at least one pesticide, where the quaternary
organosilicon surfactant of the present invention is present at an
amount sufficient to deliver between 0.005 and 2 weight percent
pesticide to the final use concentration, either as a concentrate
or diluted in a tank mix. Optionally the pesticidal composition may
include excipients, cosurfactants, solvents, foam control agents,
deposition aids, drift retardants, biologicals, micronutrients,
fertilizers and the like. The term pesticide means any compound
used to destroy pests, e.g., rodenticides, insecticides, miticides,
fungicides, and herbicides. Illustrative examples of pesticides
that can be employed include, but are not limited to, growth
regulators, photosynthesis inhibitors, pigment inhibitors, mitotic
disrupters, lipid biosynthesis inhibitors, cell wall inhibitors,
and cell membrane disrupters. The amount of pesticide employed in
compositions of the invention varies with the type of pesticide
employed. More specific examples of pesticide compounds that can be
used with the compositions of the invention are, but not limited
to, herbicides and growth regulators, such as: phenoxy acetic
acids, phenoxy propionic acids, phenoxy butyric acids, benzoic
acids, triazines and s-triazines, substituted ureas, uracils,
bentazon, desmedipham, methazole, phenmedipham, pyridate, amitrole,
clomazone, fluridone, norflurazone, dinitroanilines, isopropalin,
oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate,
sulfonylureas, imidazolinones, clethodim, diclofop-methyl,
fenoxaprop-ethyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop,
sethoxydim, dichlobenil, isoxaben, and bipyridylium compounds.
Fungicide compositions that can be used with the present invention
include, but are not limited to, aldimorph, tridemorph, dodemorph,
dimethomorph; flusilazol, azaconazole, cyproconazole,
epoxiconazole, furconazole, propiconazole, tebuconazole and the
like; imazalil, thiophanate, benomyl carbendazim, chlorothialonil,
dicloran, trifloxystrobin, fluoxystrobin, dimoxystrobin,
azoxystrobin, furcaranil, prochloraz, flusulfamide, famoxadone,
captan, maneb, mancozeb, dodicin, dodine, and metalaxyl.
Insecticides, including larvacide, miticide and ovacide compounds
that can be used with the composition of the present invention, but
not limited to, Bacillus thuringiensis, spinosad, abamectin,
doramectin, lepimeectin, pyrethrins, carbaryl, primicarb, aldicarb,
methomyl, amitraz, boric acid, chlordimeform, novaluron,
bistrifluron, triflumuron, diflubenzuron, imidacloprid, diazinon,
acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl,
azinphos-methyl, izoxathion, chlorpyrifos, clofentezine,
lambda-cyhalothrin, permethrin, bifenthrin, cypermethrin and the
like.
2. Fertilizers and Micronutrients
Fertilizers or micronutrients include, but not limited to, zinc
sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium
nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium
phosphate, urea phosphate, calcium nitrate, boric acid, potassium
and sodium salts of boric acid, phosphoric acid, magnesium
hydroxide, manganese carbonate, calcium polysulfide, copper
sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium
molybdate, calcium chloride.
The fertilizer or micronutrient may be a liquid or a solid. If a
solid, it is preferable that it is soluble in a solvent, or the
quaternary organosilicon surfactant of the present invention, prior
to application, and the silicone may act as a solvent, or
surfactant for such solubility or additional surfactants may
perform this function.
3. Agricultural Excipients
Buffers, preservatives and other standard agricultural excipients
known in the art also may be included in a composition of the
invention.
Solvents may also be included in compositions of the present
invention. These solvents are in a liquid state at room
temperature. Examples include water, alcohols, aromatic solvents,
oils (i.e. mineral oil, vegetable oil, silicone oil, and so forth),
lower alkyl esters of vegetable oils, fatty acids, ketones,
glycols, polyethylene glycols, diols, paraffinics, and so forth.
Particular solvents would be 2, 2, 4 trimethyl, 1 3 pentane diol
and alkoxylated (especially ethoxylated) versions thereof as
illustrated in U.S. Pat. No. 5,674,832, herein incorporated by
reference, or N-methyl-pyrrolidone.
4. Cosurfactants
Cosurfactants useful in the compositions herein include nonionic,
cationic, anionic, amphoteric, zwitterionic, polymeric surfactants,
or any mixture thereof. Surfactants are typically hydrocarbon
based, silicone based or fluorocarbon based.
Moreover, other cosurfactants, that have short chain hydrophobes
that do not interfere with superspreading as described in U.S. Pat.
No. 5,558,806 herein incorporated by reference are also useful.
Useful surfactants include alkoxylates, especially ethoxylates,
containing block copolymers including copolymers of ethylene oxide,
propylene oxide, butylene oxide, and mixtures thereof;
alkylarylalkoxylates, especially ethoxylates or propoxylates and
their derivatives including alkyl phenol ethoxylate;
arylarylalkoxylates, especially ethoxylates or propoxylates. and
their derivatives; amine alkoxylates, especially amine ethoxylates;
fatty acid alkoxylates; fatty alcohol alkoxylates; alkyl
sulfonates; alkyl benzene and alkyl naphthalene sulfonates;
sulfated fatty alcohols, amines or acid amides; acid esters of
sodium isethionate; esters of sodium sulfosuccinate; sulfated or
sulfonated fatty acid esters; petroleum sulfonates; N-acyl
sarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and
so forth.
Specific examples include alkyl acetylenic diols (SURFONYL--Air
Products), pyrrilodone based surfactants (e.g., SURFADONE--LP
100--Ashland), 2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates
(e.g., RHODASURF DA 530--Rhodia), ethylene diamine alkoxylates
(TETRONICS--BASF), ethylene oxide/propylene oxide copolymers
(PLURONICS--BASF), Gemini type surfactants (Rhodia) and diphenyl
ether Gemini type surfactants (e.g. DOWFAX--Dow Chemical).
Preferred surfactants include ethylene oxide/propylene oxide
copolymers (EO/PO); amine ethoxylates; alkyl polyglycosides;
oxo-tridecyl alcohol ethoxylates, and so forth.
In a preferred embodiment, the agrochemical composition of the
present invention further comprises one or more agrochemical
ingredients. Suitable agrochemical ingredients include, but not
limited to, herbicides, insecticides, growth regulators,
fungicides, miticides, acaricides, fertilizers, biologicals, plant
nutritionals, micronutrients, biocides, paraffinic mineral oil,
methylated seed oils (i.e. methylsoyate or methylcanolate),
vegetable oils (such as soybean oil and canola oil), water
conditioning agents such as Choice.RTM. (Loveland Industries,
Greeley, Colo.) and Quest.RTM. (Helena Chemical, Collierville,
Tenn.), modified clays such as Surround.RTM. (BASF), foam control
agents, surfactants, wetting agents, dispersants, emulsifiers,
deposition aids, antidrift components, and water.
Suitable agrochemical compositions are made by combining, in a
manner known in the art, such as, by mixing one or more of the
above components with the quaternary organosilicon surfactant of
the present invention, either as a tank-mix, or as an "In-can"
formulation. The term "tank-mix" means the addition of at least one
agrochemical to a spray medium, such as water or oil, at the point
of use. The term "In-can" refers to a formulation or concentrate
containing at least one agrochemical component. The "In-can"
formulation may then diluted to use concentration at the point of
use, typically in a Tank-mix, or it may be used undiluted.
5. Coating Compositions
Typically, coating formulations require a wetting agent or
surfactant for the purpose of emulsification, compatibilization of
components, leveling, flow and reduction of surface defects.
Additionally, these additives may provide improvements in the cured
or dry film, such as improved abrasion resistance, antiblocking,
hydrophilic, and hydrophobic properties. Coatings formulations may
exist as, Solvent-borne coatings, water-borne coatings and powder
coatings.
The coatings components may be employed as: architecture coatings;
OEM product coatings such as automotive coatings and coil coatings;
Special Purpose coatings such as industrial maintenance coatings
and marine coatings;
Typical resin types include: polyesters, alkyds, acrylics, epoxies
and polyurethanes.
6. Personal Care Products
In a preferred embodiment, the quaternary organosilicon surfactant
of the present invention comprises, per 100 parts by weight ("pbw")
of the personal care composition, from 0.1 to 99 pbw, more
preferably from 0.5 pbw to 30 pbw and still more preferably from 1
to 15 pbw of the quaternary organosilicon surfactant and from 1 pbw
to 99.9 pbw, more preferably from 70 pbw to 99.5 pbw, and still
more preferably from 85 pbw to 99 pbw of the personal care
composition.
The silylated surfactant compositions of the present invention may
be utilized in personal care emulsions, such as shampoo and
conditioners as well as lotions, and creams.
The personal care applications where the silylated surfactant
compositions of the present invention and the silicone compositions
derived therefrom of the present invention may be employed include,
but are not limited to, deodorants, antiperspirants,
antiperspirant/deodorants, shaving products, skin lotions,
moisturizers, toners, bath products, cleansing products, hair care
products such as shampoos, conditioners, mousses, styling gels,
hair sprays, hair dyes, hair color products, hair bleaches, waving
products, hair straighteners, manicure products such as nail
polish, nail polish remover, nails creams and lotions, cuticle
softeners, protective creams such as sunscreen, insect repellent
and anti-aging products, color cosmetics such as lipsticks,
foundations, face powders, eye liners, eye shadows, blushes,
makeup, mascaras and other personal care formulations where
silicone components have been conventionally added, as well as drug
delivery systems for topical application of medicinal compositions
that are to be applied to the skin.
In a preferred embodiment, the personal care composition of the
present invention further comprises one or more personal care
ingredients. Suitable personal care ingredients include, for
example, emollients, moisturizers, humectants, pigments, including
pearlescent pigments such as, for example, bismuth oxychloride and
titanium dioxide coated mica, colorants, fragrances, biocides,
preservatives, antioxidants, anti-microbial agents, anti-fungal
agents, antiperspirant agents, exfoliants, hormones, enzymes,
medicinal compounds, vitamins, salts, electrolytes, alcohols,
polyols, absorbing agents for ultraviolet radiation, botanical
extracts, surfactants, silicone oils, volatile silicones, organic
oils, waxes, film formers, thickening agents such as, for example,
fumed silica or hydrated silica, particulate fillers, such as for
example, talc, kaolin, starch, modified starch, mica, nylon, clays,
such as, for example, bentonite and organomodified clays.
Suitable personal care compositions are made by combining, in a
manner known in the art, such as, for example, by mixing, one or
more of the above components with the silylated surfactant
compositions. Suitable personal care compositions may be in the
form of a single phase or in the form of an emulsion, including
oil-in-water, water-in-oil and anhydrous emulsions where the
silicone phase may be either the discontinuous phase or the
continuous phase, as well as multiple emulsions, such as, for
example, oil-in water-in-oil emulsions and water-in-oil-in
water-emulsions.
In another useful embodiment, a skin care composition comprises the
silylated surfactant compositions of the present invention, and a
vehicle, such as, for example, a silicone oil or an organic oil.
The skin care composition may, optionally, further include
emollients, such as, for example, triglyceride esters, wax esters,
alkyl or alkenyl esters of fatty acids or polyhydric alcohol esters
and one or more the known components conventionally used in skin
care compositions, such as, for example, pigments, vitamins, such
as, for example, Vitamin A, Vitamin C and Vitamin E, sunscreen or
sunblock compounds, such as, for example, titanium dioxide, zinc
oxide, oxybenzone, octylmethoxy cinnamate, butylmethoxy
dibenzoylmethane, p-aminobenzoic acid and octyl
dimethyl-p-aminobenzoic acid.
In another useful embodiment, a color cosmetic composition, such
as, for example, a lipstick, a makeup or a mascara composition
comprises the silylated surfactant composition, and a coloring
agent, such as a pigment, a water soluble dye or a liposoluble
dye.
The uses of the compositions of the present invention are not
restricted to personal care compositions, other products such as
waxes, polishes and textiles treated with the compositions of the
present invention are also contemplated.
7. Home Care Products
Home care applications include laundry detergent and fabric
softener, dishwashing liquids, wood and furniture polish, floor
polish, tub and tile cleaners, toilet bowl cleaners, hard surface
cleaners, window cleaners, antifog agents, drain cleaners,
auto-dish washing detergents and sheeting agents, carpet cleaners,
prewash spotters, rust cleaners and scale removers.
The following examples are illustrative of the organomodified
silylated surfactant of the invention, its preparation, its
properties, and its use in a herbicide composition.
Example 1: Preparation of Chlorosilane Adduct
A 2000 mL four-neck round bottom flask was equipped with a magnetic
stir bar, reflux condenser with nitrogen gas inlet, thermocouple,
addition funnel and heating mantle. 3,3-Dimethyl-1-butene (170.69
g, 2.02 mol, 99.6 weight percent purity) and Karstedt's catalyst (5
ppm) were charged to the flask, at 15.degree. C. under N.sub.2. The
flask was warmed up to 35.degree. C. dimethylsilyl chloride (192.08
g, 2 mol, 98.5 weight percent purity) was charged to the addition
funnel, and added drop wise to the round bottom flask. An immediate
exotherm was noted. Addition of dimethylsilyl chloride was
continued over 2.5 hours. After addition, the reaction was
maintained at 40.degree. C. for 3 hours, and then analyzed by gas
chromatography. Found: >95 percent conversion to chlorosiliane
adduct.
##STR00003##
Example 2: Preparation of Hydride Intermediate
The chlorosilane adduct of Example 1 was cooled to 1.degree. C. A
solution of sodium dihydro-bis-(2-methoxyethoxy) aluminate
(Vitride, 61.8 weight percent in toluene; 359.83 g of solution, 1.1
mol) was charged to an addition funnel and added drop wise to the
solution of chlorosilane at a rate to maintain reaction temperature
<5.degree. C. (total addition time .about.3.5 hours). After
completion of addition, reaction mixture was stirred and slowly
allowed to warm to room temperature (.about.12 hours). Finally, to
this reaction mixture, 275 g of diethylene glycol dibutyl ether was
added and stripped under vacuum. The clear colorless product was
collected as a 50 weight percent solution in toluene. Product was
analyzed by gas chromatography and found to have undergone
quantitative conversion to the desired reduction product.
##STR00004##
Examples 3-7; Comparative Examples 1-3: Preparation of
Organomodified Monosilyl Compounds
The hydride intermediate of Example 2 was farther modified with
various allyl polyalkyleneoxides to produce organomodified
monosilyl compounds of the present invention (Table 1) as well as
several compounds outside the scope of the invention for purposes
of comparison (Table 2).
The organomodified monosilyl compounds of the present invention as
well as those prepared for comparison purposes were obtained by
conventional methods of platinum-mediated hydrosilylation, e.g., as
described in Bailey, U.S. Pat. No. 3,299,112, herein incorporated
by reference. A representative synthesis is set forth below.
A 100 mL round bottom flask was equipped with a magnetic stir bar,
reflux condenser with nitrogen inlet, thermocouple, addition funnel
and heating mantle. Allyl polyether with an avg. molecular weight
of about 350 g/mol (3.5 g; 0.01 mol), chloroplatinic acid (5 ppm)
and sodium propionate (3.5 mg) were charged to the round bottom
flask, stirred and brought to 85.degree. C. The solution of
carbosilane (Example 2) in toluene (15 g of 8 weight percent
solution; 0.00833 mol carbosilane) was charged to the addition
funnel and added drop wise to the flask. An immediate exotherm was
noted, addition was continued over 45 minutes. After complete
addition, the reaction was maintained at 85.degree. C. for 5 hours.
The reaction product was tested for Si--H content and indicated 0
cc H.sub.2/g remaining. The reaction mixture was stripped
(.about.10 mm Hg, 100.degree. C.) for 1.5 hours to remove
volatiles, allowed to cool to <40.degree. C., treated with
celite and sodium bicarbonate, stirred, pressure-filtered, and
bottled. Yield: 4 g of clear, brown color liquid.
##STR00005##
Table 1 below lists polyether-modified monosilyl compounds of the
present invention conforming to the general structure:
(CH.sub.3).sub.3C(CH.sub.2).sub.2Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub-
.2--O--(CH.sub.2CH.sub.2O).sub.a(CH.sub.2CH(CH.sub.3)O).sub.bR.sup.4
wherein subscripts a and b and group R.sup.4 are as set forth
therein.
TABLE-US-00005 TABLE 1 Compounds of the Invention Compound
subscript a subscript b R.sup.4 Ex. 3 7.5 0 CH.sub.3 Ex. 4 7.5 0 H
Ex. 5 4 0 H Ex. 6 11 0 H Ex. 7 5 2.5 H
Table 2 lists three organomodified monosilyl compounds outside the
scope of the present invention and conforming to the general
structure:
(CH.sub.3).sub.3Si(CH.sub.2).sub.2Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.su-
b.2--O--(CH.sub.2CH.sub.2O).sub.cY wherein subscript b and group Y
are as set forth therein. Each of the compounds of Comparative
Examples 1-3 differs from those of the invention in the nature of
the alkyl group bonded to the silicon atom, specifically, in having
only 4 carbon atoms in the alkyl group compared to the compounds of
the invention which must contain at least 5, and up to 8, carbon
atoms in the alkyl group.
TABLE-US-00006 TABLE 2 Comparative Organomodified Monosilyl
Compounds Comgound subscript c Y Comp. Ex. 1 7.5 CH.sub.3 Comp. Ex,
2 7.5 H Comp. Ex. 3 11 H
Example 8: Preparation of Quaternary-Modified Monosilyl Compound
(QC-1)
The following reaction scheme shows the preparation of a
quaternary-modified monosilyl compound employing known and
conventional synthesis procedures:
##STR00006## 26 g (0.1 mol) of the monoepoxy-functional monosilyl
compound shown above, 10.39 g (0.1 mol) of N, N'-dimethylamino
propanol, 13.86 g (0.1 mol) of dimethylol propionic acid and 16.75
g of dipropylene glycol solvent were charged into a 3-neck flask
provided with a condenser and nitrogen blanket. The mixture was
quickly heated to 80-82.degree. C. and continuously stirred for 18
hours. The flask was thereafter cooled to room temperature to
obtain a brown color viscous solution of the above indicated
mentioned quaternary ammonium-modified monosilyl compound
(H.sub.3C).sub.3CCH.sub.2CH.sub.2--Si(CH.sub.3).sub.2--CH.sub.2CH.sub.2CH-
.sub.2--O--CH.sub.2CH(OH)CH.sub.2N.sup.+(CH.sub.3).sub.2--CH.sub.2CH.sub.2-
CH.sub.2OH [(CH.sub.2OH).sub.2(CH.sub.3)C--COO.sup.-] at 75 wt % in
dipropylene glycol.
Example 9: Spreading Properties of Organomodified Monosilyl
Compounds R.sup.1--Si(CH.sub.3).sub.2--Z
Spreading was determined by applying a 10 .mu.L droplet, of
surfactant solution to polystyrene Petri dishes (Fisher Scientific)
and measuring the spread diameter (mm) after 30 seconds, at a
relative humidity between 50 and 70% (at 22 to 25.degree. C.). The
solution was applied with an automatic pipette to provide droplets
of reproducible volume. Deionized water that was further purified
with a Millipore filtration system was used to prepare the
surfactant solutions.
Table 3 demonstrates that the compounds of the present invention
(Examples 3-8) provide spreading properties similar to the
comparative compounds (Comparative Examples 1-3). Additionally, as
the polyethylene content increases from about 4 EO to 7.5 EO to 11
EO unites (compare results of Example 6 with Example 2), there was
a corresponding increase in spreading for the compounds of the
present invention,
TABLE-US-00007 TABLE 3 Spreading Properties of Compounds Spread
Diameter (mm); Weight % Compound Compound 0.05% 0.1% 0.2% Ex. 3 31
48 50 Ex. 4 29 46 48 Ex. 5 23 23 23 Ex. 6 6 7 7 Ex. 7 34 49 47 Ex.
8 10 21 33 Comp. Ex. 1 27 38 46 Comp. Ex. 2 30 39 44
Example 10: Hydrolytic Stability of the Organomodified
Monosilylated Compound
Hydrolytic stability was determined for a representative compound
of the present invention using spreading as an indicator of
stability. It is well known that hydrolysis of organosilicon
surfactants significantly decreases over time when exposed to a low
pH environment, e.g., pH of 3.
Spreading was determined according to the method described in
Example 1. Surfactant solutions were prepared in either deionized
water (.about.pH 5) and in a pH 3 buffer solution (Fischer
Scientific).
Table 4 demonstrates that the organomodified monosilyl compounds of
the present invention are resistant to hydrolysis at pH 3 and pH 4.
Spreading was essentially unchanged over the test period.
TABLE-US-00008 TABLE 4 Effect of pH on Hydrolysis Stability of
Organomodified Silyl Compounds Compound Initial 24h 5d 30d 90d
Comp. Ex. 1 55 52 49 nd nd Comp. Ex. 1 in pH 3 buffer 49 45 42 nd
42 Ex. 4 41 46 41 nd nd Ex. 4 in pH 3 buffer 44 39 37 47 47 Ex. 4
in pH 4 buffer 45 nd nd 47 46
Example 11: Uptake of 2,4-D-Dimethylamine Salt into Canola Leaf
The uptake of [C.sup.14]-2,4-dichlorophenoxyacetic acid,
dimethylamine salt (2,4-D DMA salt) (1% a.e./100 L/ha) was
determined in canola at 2 HAT and 24 HAT (Hours After Treatment)
according to the method described by Lui, in Pro. 18th
Asian-Pacific Weed Sci. Soc. Conf., pp. 561-566. Liu, Z Q;
2001.
Table 6 demonstrates that the organomodified monosilyl compounds of
the present invention show equivalent or improved uptake of 2,4-D
dimethylamine into canola leaf relative to the compound of
Comparative Example 1.
TABLE-US-00009 TABLE 6 Uptake of [C.sup.14]-2,4-D, DMA Salt Into
Canola Leaf Uptake % Uptake % Compound % wt/vol (2 HAT) (24 HAT)
Ex. 3 0.1% 25.3 d 63.4 abc Ex. 2 0.1% 27.4 d 64.2 ab Ex. 7 0.1%
23.7 d 54.4 c Comp. Ex. 1 0.1% 27.8 d 63.8 ab Ex. 3 0.15% 23.4 d
68.5 ab Ex. 4 0.15% 28.5 d 65.8 ab Ex. 7 0.15% 22.5 de 65.7 ab
Comp. Ex. 1 0.15% 25.5 d 59.9 be Means sharing common postscripts
are not significantly different (p = 0.05).
Example 12: Effect of Spray Droplet Adhesion on Total Available
Dose on Canola Leaf
A spray droplet was generated by a dynamic system via a spray
nozzle. The addition of a compound to a spray mixture can help
reduce surface tension allowing the droplets to adhere to the
target leaf. However, not all compounds promote the same level of
droplet adhesion and therefore only a portion of the spray adheres
to the leaf. The remaining spray may bounce off the leaf making it
ineffective for delivery of the desired agrochemical (i.e.
herbicide, fungicide, fertilizer, etc.).
The Total Available Dose (TAD) takes into consideration both
agrochemical uptake and spray droplet adhesion. The TAD is the
amount of material delivered to a plant surface (Adhesion) that is
available for Uptake in to the foliage. Essentially TAD=Uptake
(%).times.Droplet Adhesion (%). The higher the TAD the higher the
uptake potential.
Spray droplet adhesion (as a % of impacted droplets) was determined
as described previously (Stevens et al. 1993) using a piezoelectric
droplet generator with a 200 .mu.m nozzle orifice to form
mono-sized droplets of approx. 450 .mu.m. The droplet freefall
distance was 53 cm. Canola foliage (difficult-to-wet) was used as
the impaction surface, with a leaf angle of 22.5.degree..
Solutions (0.15%) of the compounds of the present invention and
that of Comparative Example 1 were prepared using deionized water.
Solutions also contained 2,4-D DMA salt (1%) as the herbicide.
Determination of the TAD used the uptake results from the previous
example (Table 7) along with the adhesion results reported in Table
6.
Table 7 below demonstrates that the organomodified monosilyl
compounds of the present invention provided similar or better
droplet adhesion on canola leaf relative to the comparative
compound. However, the compounds of the present invention provide a
higher TAD than the compound of Comparative Example 1.
TABLE-US-00010 TABLE 7 Effect of Droplet Adhesion on Total
Available Dose of 2,4-D DMA Into Canola Leaf Droplet Uptake %
Uptake % Adhesion TAD TAD Compound % wt/vol (2 HAT) (24 HAT) (%) (2
HAT) (24 HAT) None 0 12.1e 70.2 a 7.0 0.8 4.9 (2,4-D alone) Ex. 3
0.15% 23.4d 68.5 ab 97 22.7 66.4 Ex, 4 0.15% 28.5d 65.8 ab 93 26.5
61.1 Ex. 7 0.15% 22.5de 65.7 ab 91 2.8 63.7 Comp. Ex. 1 0.15% 25.5d
59.9 be 93 23.7 55.7 Means sharing common postscripts are not
significantly different (p = 0.05)
While the invention has been described with reference to particular
embodiments, those skilled in the art will understand that various
changes may be made and equivalents may be substituted for elements
thereof without departing from the scope of the invention. It is
intended that the invention not be limited to the particular
embodiments disclosed but that it include all embodiments falling
within the scope of the appended claims.
* * * * *